【作者】 李海平；

【导师】 吴文士；

【作者基本信息】 华侨大学 ， 物理化学， 2008， 硕士

【摘要】 非线性光学材料在当今高速发展的信息产业中具有广泛的应用,在光频率转换、激光调制、激光偏转、Q开关材料等方面有着十分广阔的应用前景,因此,研究此类材料对于光信号处理、光转换技术等领域具有重要的学术意义。本学位论文根据有机分子结构丰富多变的特点,利用结构-性能关系对非线性光学材料的结构要求,选择4-硝基-2-吡啶甲酸-1-氧(POA)为母体,进行改组设计,通过溶液法生长晶体,培养了6种晶体;并利用元素分析、X-射线单晶衍射、傅立叶变换红外光谱、差热与热重分析、紫外-可见光谱、荧光分析、倍频效应分析等手段对晶体材料的组成、结构和性质进行相关研究。6种晶体分为三类:1、乙吡啶醚衍生物3种: PEHA(1)(4-乙氧基-2-吡啶羟肟酸)、PEHZ(2)(4-乙氧基-2-吡啶甲酰肼)、PPEHZ(3)(4-乙氧基-N-丙酰-2-吡啶甲酰肼);2、配位化合物2种: [ZnCl(APEHZ)(H2O)]?0.5H2O(4)(APEHZ为4-乙氧基-N-乙酰-2-吡啶甲酰肼)、[ZnCl(PPEHZ)] n(5);3、吡啶二羧酸1种: DPOA(6)(2,4-二吡啶甲酸-1-氧);X-射线单晶衍射结果表明:晶体1、2、6和配合物4为平面形结构;晶体1和2结构类似,具有非心结构;配位化合物4和配位聚合物5为5配位的配合物;晶体2通过分子间氢键形成二维结构,晶体1、3、6通过分子间氢键形成一维链状结构,配位聚合物5以羧基氧为桥和分子内氢键聚合成一维链状结构。红外光谱分析测试表明:配位化合物4和配位聚合物5中一个N-H的伸缩振动峰和弯曲振动峰消失;配位化合物4和配位聚合物5中烷酰基部分C=O的伸缩振动峰发生红移;配位聚合物5酰肼基部分C=O的伸缩振动峰也发生红移。紫外-可见光谱测试表明:晶体1、2、3的紫外吸收峰位置类似;晶体6的吸收峰位置与晶体1、2、3相比较均发生了红移,并且透光波段变窄。差热与热重分析测试表明:晶体6的热稳定性高于POA,分解温度提高了近30℃;晶体1、2、3的热稳定性与POA相比稍差;配位聚合物5骨架分子的分解温度比配位化合物4的高。荧光测试结果说明:晶体6的发射波长与POA相比较发生了蓝移;晶体1、2、3的激发光谱和发射光谱基本一致;配位化合物4的发射光谱与其配体的发射光谱相比较发生了红移。非线性光学性质测试表明,晶体1的1.06μm激光二倍频光强度是KDP的2倍;晶体2的1.06μm激光二倍频光强度较弱。更多还原

【Abstract】 Nonlinear Optical (NLO) materials have extensive applications in the high-speed developing information industry, and they play a more and more important part in the application areas of frequency-changing, laser modulation and deflexion, and Q switch and so on. So it is very important for the light-signal processing, transferring and operation and so on to research NLO materials. Based on the flexibility of organic molecule structure, we picked 4-Nitro-1-Oxide-Pyridine-2-Carboxylic Acid(POA) as a mother reagent to prepare and synthesized 6 crystal materials through solution growth technique, in fitting of the requirements for NLO materials from the relationship between molecular structure and material function. The grown 6 crystals were characterized using Element analysis, Single-crystal X-ray diffraction, FTIR, UV-visible, DSC-TGA, Fluorescence, SHG studies.Crystal 1, 2 and 3 are Ethylpyridl ether derivatives, and crystal 4 and 5 are complexes, and crystal 6 belongs to pyridine dicarboxylic acid. Single-crystal X-ray analysis shows, crystal 1, 2, 6 and complex 4 have plane-structure, and crystal 1 and 2 have the similar noncentrosymmetrical structure, and complex 4 and 5 have five-coordination structure, and the packing arrangement with intermolecular hydrogen bonds of crystal 2 is two-dimensional structure but one-dimensional structure in crystal 2, 3 and 6 is formed through the intermolecular hydrogen bonds, and there is a one-dimensional structure in complex 5 through an atom of O in carboxyl and an intramolecular hydrogen bond. FTIR analysis shows that the stretching and bending peaks of N-H and the stretching peaks of C=O in complex 4 and 5 disappear. UV-visible analysis shows that absorbing peaks of crystal 6 have red-shift phenomenon compare to that of crystal 1, 2 and 3 with the similar absorbing peaks and that there is a higher cutoff ultraviolet-visible absorption of crystal 6 than that of crystal 1, 2 and 3. DSC-TGA analysis shows that the stability of crystal 6 is 30℃higher than that of POA but the stability of crystal 1, 2 and 3 is lower than that of POA and that the decomposition temperature of framework molecular of complex 5 is higher than that of complex 4. Fluorescence analysis shows that emission peak of crystal 6 has blue-shift phenomenon compare to that of POA and crystal 1, 2 and 3 have the similar excitation and emission peaks, and that emission peak of complex 4 has red-shift phenomenon compare to organic ligand. SHG studies shows that SHG efficiency of crystal 1 is about 2 times as large as that of KDP and that crystal 2 has weak SHG efficiency.更多还原